Water-soluble disazo dyes containing two thiosulfuric acid groups



United States Patent The present invention relates to new water-solubleazodyestntfs containing one or more thiosulfuric acid groups and to aprocess for preparing them; more particularly it relates to dyestuifs ofthe following general formula in which one X on each of the benzenerings stands for hydrogen and the other X for hydrogen, methyl, methoxyor chlorine, one Y stands for hydrogen or methoxy and the other Y standsfor hydrogen, methyl, methoxy or chlorine, and Me represents an alkalimetal or ammonium.

We have found that aromatic amines containing one or more thiosulfuricacid groups bound to the aromatic nucleus, via bridge membersinterrupted by hetero atoms, can be diazotized and reacted withcompounds capable of being coupled to obtain azo-dyestulfs soluble inwater.

It was 'known that compounds containing thiosulfuric acid groups areconverted into disulfides by oxidizing agents such, for example, asiodine. Since nitrous acid liberates iodine from iodides, it could beassumed that nitrous acid forms also disulfides when acting on compoundscontaining thiosulfuric acid groups. The more surprising is theobservation that aromatic amines containing thiosulfuric acid groups canbe diazotized without diificulty and without the formation ofdisulfides. The only exception are the ortho-amino-aryl-thiosulfuricacids and the substitution products thereof, since these compounds areconverted during the diazotization into noncouplingortho-arylene-diazo-sulfides (German Patent 120,540). Thepara-amino-phenylthiosulfuric acid obtainable according to German Patent120,540 is said to be diazotiz'able but actually yields the4,4'-diamino-diphenyldisulfide which is diazotizable as could beexpected (J. Chem. Soc. London, 1930, 2691).

Due to the sensitivity of the thiosulfuric acid groups, theamino-aryl-thiosulfuric acids are diazotized in the cold, preferably ata temperature ranging from 0 C. to +5 C. Such amino-aryl-thiosulfuricacids that are diflicultly soluble in water, can be indirectlydiazotized by introducing them in the form of their easily solublealkali metal salts in admixture with alkali nitrite into an acid. Insome 3,098,064 Patented July 16, 1963 cases it is advisable to carry outthe diazotization with the use of organic solvents soluble in watersuch, for example as acetone. The diazonium salts of aryl-thiosulfuricacids obtained in this manner frequently crystallize as hybrid ions inthe form of interior salts.

Depending on their constitution the diazotized aminoaryl-thiosulfuricacids are reacted with compounds capable of being coupled in an acid,neutral or alkaline solution, and the azo-dyestufis thus obtained whichare easily soluble in water are isolated by the addition of salt.

The water-soluble azo-dyestufi's obtained by the process of the presentinvention which contain, for example, 1 to 4 thiosulfuric acid groups inthe molecule are advantageously prepared in the form of their well'crystallizing alkali metal or ammonium salts, since the dyestuffscontaining free thiosulfuric acid groups tend to instability unless theyare obtained as inner salts. The dyestuffs are suitable for dyeing andprinting wool, silk, leather, polyamides or polyurethanes from an acidbath and yield yellow, orange, red, brown, blue and green dyeings whichmostly possess good properties of fastness.

The following serve to illustrate the invention but they are notintended to limit it thereto, the parts being by weight unless otherwisestated, and the relationship of parts by Weight to parts by volume beingthe same as that of the kilogram to the liter:

A solution of 18.7 parts of3-amino-benZene-sulfonylamino-fl-ethyl-thiosulfuric acid and 6 parts ofsodium bicarbonate in parts by volume of water to which 4.4 parts ofsodium nitrite have been added, is run at 0 C. into a mixture of 24parts by volume of concentrated bydrochioric acid and 100 parts byvolume of water. The suspension of the diazonium salt thus prepared isadjusted to a pH value of 5 to 6 by means of sodium bicarbonate. Intothis suspension is then run a solution of 10 parts 1,4di-(acetoacetylamino)-2-chloro-5-methoxybenzene in 50 parts by volume ofwater and 5 parts by volume of a sodium hydroxide solution of 33%strength. The mixture is brought into a stirrable state by the additionof acetone and heated to 60 C. whereby the dyestuif formed is obtainedin crystalline form. It is filtered oif and dried at 60 C. The dyestuffdyes wool fast greenish yellow tints.

The dyestuffs listed in the following table were prepared in likemanner. They yield on natural protein fibers, such as wool and silk, andon polyamide and polyurethane fibers dyeings which possess a very goodfastness to wet processing.

Diazo Component Coupling Component Tint 3 amino benzyl thiosulfuric 1,4di- (aeetoaeetylamino) greenish acid. benzene. yellow.

4 amino benzene sulfonyl do reddish amino B ethyl thiosulfu yellow. rioacid.

3 amino 6 chloro -benzeue do Do.

sulionyl amino 1S ethyl thiosulfuric aeid.

3-amino-benzene-sulionyldo greenish (methylamino)-fl-ethylyellow.thiosulfuric acid.

4-amino-benzoylamino-B- do golden ethyl thiosulfurlc acid. yellow.

3-amino-benzenesulfonyldo reddish amilno-fi-ethyl-thiosulfurie yellow.ac1

D0 1,4-di-(acetoacetylamino)- greenish 2-chloro-5-methoxy yellow.benzene.

3. A dyestuff of the formula Diazo Component Coupling Component TintOH1-CO-CHN=N- S O z-NHCH2-C H2SS O aNa B-amino-benzyl-thiosuliuric1,4-di-(acetoacetylamino)- golden acid. 2-chl0ro-5-methoxy yellow. 0110- benzene. NH 3-amino-G-methyl-benzenedo greenishsulfonylamino-fl-ethylyellow. thiosuliuric acid. 0 CH3-amino-4-metl1oxy-benzenedo golden sulfonylamino-fl-ethylyellow.thiosulfuric acid. 3-amino-benzene-sulionyldo greenish 1O(cyano-ethyl-amino)-B- yellow. 1 ethyl-thiosulfuric acid. NH4-arnino-benzoylamino-B- 1,4-di-(aeetoacctylamino)- Do.

ethyl-thiosulfuric acid. 2-chloro-benzene. C 03-amino-4-methoxy-benzene- .do Do.

sulfonylarnlno fl-ethyl- O H3CO- O HN=N -S O nNI-I- 0 H2 C Hz-SS O aNnthiosuliurie acid.

Do 2,5-di-(acetoacetylamino)- golden toluene. yellow C11 03-amino-benzene-sulionyldo yellow.

(methylamino)-B-ethylthiosulfuric acid. 4. A dyestuif Of the formula3-amino-benzene-sulionyldo golden amino-fl-ethyl-thiosuliurieyellowacid. CH COCH--N=N -SO2NHCH2CH2S-SO3N8 Do 2,5-di-(acetoacetylamino)- Do.

anisol. O0 3-amino-4-methoxy-benzenedo Do. I 01130--sulionylamino-fl-ctliyl-thlo- NH sulfuric acid.3-amino-benzene-sulfonyldo yellow.

(methylamino)-B-ethyl- 0 Ha thiosuliuric acid.3-amino-4-methoxy-bcnzene- 2,5-di-(acetoacetylamino)- goldensulionylamino-flethylhydroquinone-dimethyl orange. thiosuliurlc acid.ether. 3-amino-benzene-sulfonyldo Do.

amino-fl-ethyl-thiosul- NH iuric acid. CH

30 (I10 CH CO-CHN=N SO2NECH2CH2SSO3N3 We claim: 1. Water-solubledisazo-dyestuffs of the formula 5. A dyestufi of the formula CaCO(!3HN=N -SO1-NHCHzCHiSSO3Me CH CO(3H-N=N SO2NHCHz-CH2SSO:N&

CO CO 1 X X NE NH OOH3 Y CH O- I IH I H N l X- X (I? 0 C O I CH COOHN=NSOaNH-CH2CHz-SSO;1\I8 c 0 c1-1 s0 11 H 0H, s so,N

wherein one X on each of the benzene nuclei stands for The dyfistllfi of1116 fofmulfli hydrogen and the other X for a member of the group Hconsisting of hydrogen, methyl, methoxy and chlorine, Z one Y stands fora member of the group consisting of ()0 hydrogen and methoxy and theother Y for a member I NH of the group consisting of hydrogen, methyl,methoxy and 1 chlorine, and Me represents a member of the group cono1sisting of alkali metals and ammonium.

2. A dyestuif of the formula CH;CO-OHN=N SOzNHCH2GH1-SSO Na L o 10 I CHCOI(1JTN=N SO2NHCI IzCI-IzSSOaNa References Cited in the file of thispatent L UNITED STATES PATENTS l 2,245,971 Felix et a1 June 17, 1941 v2,283,326 Felix et a1. May 19, 1942 CHPCOP'CIPIPN 2,706,200 Lecher et a1Apr 12 1955 FOREIGN PATENTS 490,945 Great Britain Aug. 24, 1938

1. WATER-SOLUBLE DISAZO-DYESTUFFS OF THE FORMULA